EP1242036B1 - Use of nanoscale active anti-dandruff ingredients - Google Patents

Abstract

The invention relates to nanoscale active anti-dandruff ingredients having a particle diameter ranging from 10 -500 nm in the production of hair-cosmetic preparations.

Description

The invention is in the field of nanoparticles and relates to the use of nanoscale anti-dandruff active ingredients in hair cosmetic preparations.

State of the art

A large number of hair cosmetic preparations containing anti-dandruff active ingredients are known from the prior art. However, the effect of these anti-dandruff agents is always related to the distribution on the scalp and speed with which the compounds are incorporated, absorbed or resorbed. There is still a considerable room for improvement for the available substances of the state of the art.

WO98 / 41505 describes a process for the preparation of pyrithione salts in the submicron range, ie in a range below 1000 nm. The process is carried out in a "pressurized turbulent flow reactor that generates pulverizing forces" (claim 1) and provides particles in the range of 30-950 nm (claim 24). The particles thus produced have a better biocidal activity. These particles are not encased.
US 4,670,430 relates to zinc salts of 2-mercaptopyridine N-oxide wherein less than 50% of the particles have an average particle size of 200 nm and antibacterial compositions based on these particles. The particles are not sheathed.
WO 97/114407 relates to a method for the production of microparticles up to 300 nm, by dissolving a water-insoluble biologically active compound in a solvent and spraying this solution in the presence of surface-modifying substances in a compressed gas, a liquid or a supercritical fluid. The object of this application was to provide drugs which have improved pharmacokinetic properties, in oral and intravenous administration.

The object of the invention has thus been to accelerate the uptake of anti-dandruff active ingredients in their application by providing new dosage forms. Furthermore, they should show a long-lasting effect after application, have a good dermatological compatibility and are characterized by excellent stability during temperature storage.

Description of the invention

The invention relates to the use of specific nanoscale anti-dandruff active ingredients, which are coated with a protective colloid, with particle diameters in the range of 10 to 500 nm for the preparation of hair cosmetic preparations.

The stability of hair cosmetic preparations, such as rinses and shampoos, is increased and their effectiveness is significantly accelerated and improved by the addition of anti-dandruff active ingredients when they are in the form of nanoparticles, i. Particles having an average diameter in the range of 10 to 500, preferably 50 to 300 and in particular 100 to 150 nm. At the same time, such preparations show good dermatological tolerances.

Antidandruff agents

Anti-dandruff agents used include Piroctone Olamine (1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2- (1H) -pyridinone monoethanolamine salt), Baypival® (climbazole), Ketoconazole®, (4-acetyl-1 - {- 4- [2- (2,4-dichlorophenyl) r-2- (1H-imidazol-1-ylmethyl) -1,3-dioxylan-c-4-ylmethoxyphenyl} piperazine, selenium disulfide, Sulfur colloidal, sulfur polyethyleneglycol sorbitan monooleate, sulfur trizinol polyethoxylate, Schwfelteer distillates, salicylic acid (or in combination with hexachlorophene), undeylenic acid monoethanolamide sulfosuccinate Na salt, Lamepon® UD (protein undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione / dipyrite magnesium magnesium sulfate. Preferably, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2- (1H) -pyridone-monoethanolamine salt, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl ) -2- (1H) -pyridone-monoethanolamine salt, Magnesiumpynthion / Dipyrithion magnesium sulfate, selenium disulfide, Zinkpyrithion and / or climbazoles used.

Production of nanoparticles

• (a) die Ausgangsstoffe unter überkritischen oder nahekritischen Bedingungen in einem geeigneten Lösungsmittel löst,
• (b) die fluide Mischung über eine Düse in ein Vakuum, ein Gas oder eine Flüssigkeit entspannt, und
• (c) das Lösemittel dabei gleichzeitig verdampft.

A process for the production of nanoparticles by rapid expansion of supercritical solutions (RESS) , for example, from the article by S.Chihlar, M.Türk and K. Schaber in Proceedings World Congress on Particle Technology 3, Brighton , 1998 known. In a preferred embodiment of the invention, nanoscale anti-dandruff active ingredients are used which are obtained by reacting

• (a) dissolving the starting materials under supercritical or near-critical conditions in a suitable solvent,
• (B) the fluid mixture through a nozzle in a vacuum, a gas or a liquid relaxed, and
• (c) the solvent evaporates at the same time.

In order to prevent the nanoparticles from caking again, the starting materials are dissolved in the presence of suitable protective colloids and / or the critical solutions are dissolved in aqueous and / or alcoholic solutions of the protective colloids or in cosmetic oils, which in turn contain dissolved protective colloids. Suitable protective colloids are e.g. Gelafins, casein, gum arabic, lysalbinic acid, starch, and polymers such as polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates. Usually, the protective colloids in amounts of 0.1 to 20, preferably 5 to 15 wt .-% - based on the antidandruff agents - used.

Another suitable method for producing the nanoscale particles is the evaporation technique. In this case, the starting materials are first dissolved in a suitable organic solvent (for example alkanes, vegetable oils, ethers, alcohols, esters, ketones, acetals and the like). Thereafter, the solutions are so added in water or other non-solvent, optionally in the presence of a surface-active compound dissolved therein, that it is replaced by the Homogenization of the two immiscible solvents to precipitate the nanoparticles comes, wherein the organic solvent is preferably evaporated. Instead of an aqueous solution, O / W emulsions or O / W microemulsions can also be used. The surface-active compounds used are the protective colloids already explained in the introduction. Another possibility for the production of nanoparticles is the so-called GAS process (gas anti-solvent recrystallization). The process uses a highly compressed gas or supercritical fluid (eg, carbon dioxide) as a non-solvent to crystallize solutes. The compressed gas phase is introduced into the primary solution of the starting materials and absorbed there, whereby the liquid volume increases, the solubility decreases and finely divided particles are separated out. Similarly suitable is the PCA process (precipitation with a compressed fluid anti-solvent). Here, the primary solution of the starting materials is introduced into a supercritical fluid, which form finely divided droplets in which run off diffusion processes, so that a precipitation of very fine particles takes place. In the PGSS (Particles from Gas Saturated Solutions) process, the starting materials are melted by pressing on gas (eg carbon dioxide or propane). Pressure and temperature reach near or supercritical conditions. The gas phase dissolves in the solid and causes a lowering of the melting temperature, the viscosity and the surface tension. When expanding through a nozzle, cooling effects cause the formation of very fine particles.

Industrial Applicability

Compared to antidandruff active ingredients of the prior art, the particular fineness of the particles causes increased stability and consistency of the hair cosmetic preparations. They can be used for the preparation of cosmetic preparations for hair care. The amount used of the anti-dandruff active ingredients is usually of the order of 0.01 to 10, preferably 0.2 to 5 and in particular 0.5 to 2 wt .-% - based on the preparations.
The cosmetic preparations can furthermore be used as further auxiliaries and additives mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescing agents, bodying agents, thickeners, silicone compounds, fats, waxes, biogenic agents, deodorants, film formers, swelling agents, antioxidants, hydrotropes, preservatives, solubilizers, perfume oils , Dyes and the like.

Typical examples of suitable mild, ie particularly skin-friendly surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ethercarboxylic acids, alkyloligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter being preferred based on wheat proteins.

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids with linear C ₆ -C ₂₂ -fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, Myristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, lsostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, O-leyloleat, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucic acid stearate, erucyl oleate, erucyl behenate and erucyl erucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerdiol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / Triglyceridmisungen based on C ₆ -C ₁₈ fatty acids, esters of C ₆ C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils , branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, guerbet carbonates, esters of benzoic acid with lin earen and / or branched C ₆ -C ₂₂ -alcohols (eg Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic Hydrocarbons such as squalane, squalene or dialkylcyclohexanes into consideration.

• ➢ Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe sowie Alkylamine mit 8 bis 22 Kohlenstoffatomen im Alkylrest;
• ➢ Alkyl- und/oder Alkenyloligoglykoside mit 8 bis 22 Kohlenstoffatomen im Alk(en)ylrest und deren ethoxylierte Analoga;
• ➢ Anlagerungsprodukte von 1 bis 15 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• ➢ Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Ricinusöl und/oder gehärtetes Ricinusöl;
• ➢ Partialester von Glycerin und/oder Sorbitan mit ungesättigten, linearen oder gesättigten, verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• ➢ Partialester von Polyglycerin (durchschnittlicher Eigenkondensationsgrad 2 bis 8), Polyethylenglycol (Molekulargewicht 400 bis 5000), Trimethylolpropan, Pentaerythrit, Zuckeralkoholen (z.B. Sorbit), Alkylglucosiden (z.B. Methylglucosid, Butylglucosid, Laurylglucosid) sowie Polyglucosiden (z.B. Cellulose) mit gesättigten und/oder ungesättigten, linearen oder verzweigten Fettsäuren mit 12 bis 22 Kohlenstoffatomen und/oder Hydroxycarbonsäuren mit 3 bis 18 Kohlenstoffatomen sowie deren Addukte mit 1 bis 30 Mol Ethylenoxid;
• ➢ Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß DE 1165574 PS und/oder Mischester von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, Methylglucose und Polyolen, vorzugsweise Glycerin oder Polyglycerin.
• ➢ Mono-, Di- und Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate und deren Salze;
• ➢ Wollwachsalkohole;
• ➢ Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
• ➢ Polyalkylenglycole sowie
• ➢ Glycerincarbonat.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl group and Alkylamines having 8 to 22 carbon atoms in the alkyl radical;
• ➢ alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs;
• Adducts of 1 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• ➢ addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;
• Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
• Partial esters of polyglycerol (average intrinsic degree of condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg sorbitol), alkylglucosides (eg methylglucoside, butylglucoside, laurylglucoside) and polyglucosides (eg cellulose) with saturated and / or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and / or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
• ➢ mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.
• ➢ Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• Wool wax alcohols;
• ➢ polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• ➢ Polyalkylene glycols as well
• ➢ Glycerine carbonate.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols or castor oil are known, commercially available products. These are mixtures of homologues whose mean degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out corresponds. C _12/18 fatty acid _mono- and diesters of addition products of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl oligoglycosides, their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably approximately 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid, Isostearinsäurediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linolsäurediglycerid, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, Erucasäurediglycerid, Tartaric acid monoglyceride, tartaric acid, citric acid monoglyceride, citron diglyceride, malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may contain minor amounts of triglyceride subordinate to the manufacturing process. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said Partialglyceride.

As sorbitan sorbitan, Sorbitansesquüsostearat, Sorbitandüsostearat, Sorbitantrüsostearat, sorbitan monooleate, sorbitan, sorbitan, Sorbitanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat, Sorbitansesquitartrat, Sorbitanditartrat, Sorbitantritartrat come , Sorbitan monocitrate, sorbitan siccitrate, sorbitan di-citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan adipate, sorbitan trimaleate, and technical mixtures thereof. Also suitable are addition products of 1 to 30, preferably 5 to 10 moles of ethylene oxide to said sorbitan esters.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® GI 34), polyglyceryl-3 oleates, diisostearoyl polyglyceryl-3 diisostearates (Isolan ® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl -3 distearates (Cremophor® GS 32) and polyglyceryl polyricinoleates (Admul® WOL 1403) polyglyceryl dimerate isostearates and mixtures thereof.
Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, which are optionally reacted with from 1 to 30 mol of ethylene oxide.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylammoniumglycinat, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyldimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethytimidazoline each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine . Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C _8/18 -alkyl or -acyl group in the Molecule at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, Kokosacytaminoethylaminopropionat and C _12/18 acyl sarcosine.

As superfatting agents, substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fetters such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates having a total of at least 24 carbon atoms, especially laurone and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethylcellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopols ® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkytoligoglucosides and electrolytes such as saline and ammonium chloride.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, Methyl vinyl ether / maleic anhydride copolymers and their esters, unvarnished and polyols crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / Vinylcaprolactam terpolymers and optionally derivatized cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can also be found in Todd et al. in Cosm.Toil. 91 , 27 (1976).

Typical examples of fats are glycerides, as waxes include natural waxes, such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, Zuckeffohrwachs, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin , Ozokerite (groundwax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes in question.
Biogenic active ingredients are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Cosmetic deodorants (deodorants) counteract, cover or eliminate body odors. Body odors are caused by the action of skin bacteria on apocrine sweat, forming unpleasant-smelling degradation products. Accordingly, deodorants contain active ingredients which act as antimicrobials, enzyme inhibitors, odor absorbers or odor maskers and antiperspirants.

As germ-inhibiting agents are basically all effective against Gram-positive bacteria substances such. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3,4-dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro 3,5-dimethylphenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4 Chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, Famesol, phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as. Salicylic acid n-octylamide or salicylic acid n-decylamide.

For example, esterase inhibitors are suitable as enzyme inhibitors . These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyltrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Cognis GmbH, Dusseldorf / FRG). The substances inhibit the enzyme activity and thereby reduce odors. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Adipic acid monoethyl ester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.

Suitable odor absorbers are substances that absorb and largely retain odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce their propagation speed. It is important that perfumes must remain undisturbed. Odor absorbers have no activity against bacteria. They contain, for example, as a main component of a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known in the art as "fixatives", such. B. Extracts of Labdanum or Styrax or certain Abietinsäurederivate. Odor maskers are fragrances or perfume oils which, in addition to their function as odor maskers, give the deodorants their respective scent. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and twigs, as well as resins and balsams. Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citrate, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone and methyl cedryl ketone, the alcohols anethole, citronellol, Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg

Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, Evernyl, lreralde gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, lrotyl and Floramat alone or in mixtures.

• ➢ adstringierende Wirkstoffe,
• ➢ Ölkomponenten,
• ➢ nichtionische Emulgatoren,
• ➢ Coemulgatoren,
• ➢ Konsistenzgeber,
• ➢ Hilfsstoffe wie z. B. Verdicker oder Komplexierungsmittel und/oder
• ➢ nichtwässrige Lösungsmittel wie z. B. Ethanol, Propylenglykol und/oder Glycerin.

Antiperspirants (antiperspirants) reduce the formation of sweat by influencing the activity of eccrine sweat glands and thus counteract underarm wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

• ➢ astringent active substances,
• ➢ oil components,
• ➢ nonionic emulsifiers,
• ➢ coemulsifiers,
• ➢ Consistency provider,
• ➢ auxiliaries such. B. thickener or complexing agent and / or
• ➢ non-aqueous solvents such. As ethanol, propylene glycol and / or glycerol.

• ➢ entzündungshemmende, hautschützende oder wohlriechende ätherische Öle,
• ➢ synthetische hautschützende Wirkstoffe und/oder
• ➢ öllösliche Parfümöle.

Salts of aluminum, zirconium or zinc are especially suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds z. With propylene glycol-1,2. Aluminiumhydroxyallantoinat, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds z. With amino acids such as glycine.
In addition, antiperspirants may contain customary oil-soluble and water-soluble adjuvants in smaller amounts. Such oil-soluble auxiliaries may be, for example:

• ➢ anti-inflammatory, skin-protecting or fragrant essential oils,
• ➢ synthetic skin-protecting agents and / or
• ➢ oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives, water-soluble perfumes, pH adjusters, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural or water-soluble thickeners synthetic polymers such as xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Further suitable polymers or swelling agents can be reviewed by R. Lochhead in Cosm.Toil. 108 , 95 (1993) .

• ➢ Glycerin;
• ➢ Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• ➢ technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• ➢ Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• ➢ Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• ➢ Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• ➢ Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• ➢ Aminozucker, wie beispielsweise Glucamin;
• ➢ Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

To improve the flow behavior, it is also possible to use hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• ➢ glycerin;
• ➢ alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• Technical Oligoglyceringemische with an intrinsic degree of condensation of 1.5 to 10 such as technical Diglyceringemische with a diglycerol content of 40 to 50 wt .-%;
• ➢ Methyolverbindungen, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• ➢ Niedrigalkylglucoside, in particular those with 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;
• ➢ sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol,
• ➢ sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• ➢ Amino sugars, such as glucamine;
• Dialcohols, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation.

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore come animal raw materials in question, such as Zibet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as flavoring components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, tangerine oil, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, fixolide NP, evemyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, irotyl and floramate alone or in mixtures.

As dyes , the substances suitable and suitable for cosmetic purposes can be used, as compiled, for example, in the publication "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.
The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

Examples

To produce the nanoscale metal soaps (Examples 1 to 6) , carbon dioxide was first taken from a reservoir at a constant pressure of 60 bar and purified by means of a column with an activated carbon and a molecular sieve packing. After liquefaction, the CO _{2 was} compressed by means of a diaphragm pump at a constant delivery rate of 3.5 l / h to the desired supercritical pressure p. Subsequently, the solvent was brought to the required temperature T1 in a preheater and passed into an extraction column (steel, 400 ml), which was loaded with the waxes. The resulting supercritical, ie fluid mixture was sprayed via a laser-drawn nozzle (length 830 .mu.m, diameter 45 .mu.m) at a temperature T2 in a plexiglass expansion chamber containing a 4 wt.% Aqueous solution of an emulsifier or protective colloid. The fluid medium evaporated and left behind in the protective colloid, dispersed nanoparticles. The process conditions and the average particle size range (determined photometrically by the 3-WEM method) are given in Table 1 below. <b><u> Table 1: </ u> Nanoparticles </ b> Ex. polymer Solv p. bar T1 ° C T2 ° C Emulsifier / protective colloid PGB nm 1 Zinc pyrithione CO ₂ 200 80 175 polyvinyl alcohol 60-120 2 Octopirox® CO ₂ 180 70 160 Polyethylene glycol (M = 400) 75-120 3 Ketokonazol® CO ₂ 200 85 180 polyvinyl alcohol 75-130 4 selenium disulphide CO ₂ 200 85 175 polyvinyl alcohol 60-140 5 Magnesium bispyrithione CO ₂ 200 85 175 polyvinyl alcohol 55-140 6 Baypival® CO ₂ 200 85 175 polyvinyl alcohol 60-140

Tables 2 and 3 below contain a number of formulation examples with anti-dandruff nanoparticles.

Claims (5)

1. The use of nanoscale antidandruff agents with particle diameters of 10 to 500 nm for the production of cosmetic hair-care preparations.
2. The use claimed in claim 1, characterized in that antidandruff agents selected from the group consisting of 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinone monoethanolamine salt, climbazole, 4-acetyl-1-{4-[2-(2,4-dichlorophenyl) r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, sulfur tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid monoethanolamide sulfosuccinate sodium salt, protein/undecylenic acid condensate, zinc pyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithione magnesium sulfate are used.
3. The use claimed in claims 1 and/or 2, characterized in that 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinone monoethanolamine salt, magnesium pyrithione/dipyrithione magnesium sulfate, selenium disulfide, zinc pyrithione and/or climbazole are preferably used.
4. The use claimed in at least one of claims 1 to 3, characterized in that antidandruff agents obtained by

   (a) dissolving the starting materials in a suitable solvent under supercritical or near-critical conditions,

   (b) expanding the fluid mixture through a nozzle into a vacuum, a gas or a liquid and

   (c) simultaneously evaporating the solvent

   
   are used.
5. The use claimed in at least one of claims 1 to 4, characterized in that nanoparticles coated with a protective colloid are used.